Esters of hydroxy acetylated blown ricinoleic acid compounds with oxyalkylated phenol aldehyde resins



Patented Jan. 8, 1952 RICINOLEIC ACID COMPOUNDS WITH OXYALKYLATED PHENO LU ALD EIHYDE RESINS Melvin De Groote, St. Louis, and Bernhard 'Keiser, Webster Groves, Mo., assignors to'Petrolite Corporation, Ltd Wilmington, Del., a corporation of Delaware No Drawing. Application December 10, 1948,

Serial No. 64,449

12 Claims.- 1

, The present "invention is concerned with certain new chemical products, compounds or compositions, having useful applications in various arts; This invention is a continuation-in-part of our cO-pending application, S-erial'No. "734,203,

filedMarch l2, 194?,andnow abandoned. Itincludes methods or procedures for'manuiacturing said new products, compounds or compositions, as Well'as the products, compounds or compositions themselves.

Said new compositions are esters'inwhichthe acyl radicalis that of the fatty acid of a hydroxyacetylated drastically-oxidized dehydrated ricinoleic acid compound selected from the class consisting of drastically-oxidizeddehydrated castor oil, drastically-oxidized dehydrated triricinolein, drastically-oxidized dehydrated diricinolein, drastically-oxidized dehydrated monoricinolein, drastically-oxidized dehydrated ricinoleic acid, drastically-oxidized dehydrated polyricinoleic acid, and the estolides of drastically-oxidized destantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and notmore than 12 carbon atoms and substituted in the 2,4,6 position; said oxyalkylated resin being characterized by the introduction into the resin molecule of a plurality of divalent radicals having the formula (R10)n, in which R1 is a member selected from the class consisting of ethylene radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n' is a numeral varying from 1 to 20; with the proviso that at least 2. moles of alkylene oxide be introduced for each phenolicnucleus. V

Although the-herein described products have a number of industrial applications, they are-of particular value for resolving petroleum emulsionsof the water-in-oiltype that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in'amore or less permanentstatethroughout the oil which constitutes the continuous phase-,ofthe emulsion. llhis specific application is described and claimed in our. coo-pending. application, Serial No. 64-5148, filed December '10, .1948, "nowPatent No. 2,541,993, issued February 20,1951. See also our .coepending application, Serial No. 64,469,, filedDecember 10,-19.478.

' The new products ,arezuseiul ,as wetting, ,detergent. and level-ling agents :in the laundry, :textile and dyeing industries; :as wetting agents ,and ,detergentsin the acid .washingiof building stone and brick; as wetting agents and spreaders in :the application of asphalt in road building and the like; as a flotation reagent in the flotation sep arationpf various aqueous suspensions containing negatively ;charged particles such asisewage, coal washing waste water, and various trade wastes and the like; as .germicides,insecticides,

emulsifying agents, as for example, for cosmetics, spray oils, Water-repellent textile finishes; as lubricants, etc. 7

The oxyalkylated resins, used to provide :the alcoholic radical of the new esters, are described in our. Patents 2,499,370, granted March .7, 1950, and 2,541,991,,granted February20, 1,951, and reference is made to those patentsfor a description of the phenol-aldehyde resins used and their oxyalkylation to produce the alcoholic products. For. specific examples of the resins, reference is made to Examples. 1a through 103a of Patent 2,499,370. For examples of the oxyalkylated products, reference is made to Examples lb through 18b of Patent 2,499,370 and to the tables which appear in columns 51 through 56 thereof, and also is made to the tables which appear at col,- umns 31 through 46 of Patent 2,541,991. The'hydroxyacetylated drastically-oxidized dehydrated ricinoleic acid compounds whichprovidertheacyl radicalsliof'the newestersare described in detail iniPatent.2,375,531,:granted Mayv 8, 11945; and-reference is=made to that patent fora description of these products Forspecific examples of these products reference is Lmade to Examples through 5 ofithatpatent. i

It will be noted that having obtained-a compound which is essentially apolyhydric'alcohol, i. e.,.an oxyalkylated resin ofthe type herein contemplatedone can-produce esters by any one of the various procedures employed for producing esters of detergent-forming acids of the common polyhydric alcohols. As is well known, one may employ not only the fatty acid itself, but also any suitable derivative thereof, for instance, the acylchloride, the anhydride, etc. In some instances, trans-esterification or cross-esterification will be employed; for instance, the oxyalkylated derivatives can be heated with the methyl or ethyl ester of the selected acid or selected hydroxyacetylated, drastically-oxidized compound, in presence of the alkaline catalyst, so as to eliminate methyl or ethyl alcohols. Transesterification or cross-esterification can be employed in connection with a glyceride such as the use of hydroxyacetylated, drastically-oxidized dehydrated castor oil with the formation of glycerine, which, under conditions of reaction, probably polymerizes to give polyglycerols, and thus gives a significant and many times a major proportion of the desired ester. As to a rather complete review of the preparation of polyhydric alcohol esters of fatty acids, see Chemical Review, 33, 257-349 (1943).

Example 141 An acidic hydroxyaoetylated, drastically-oxidized dehydrated ricinoleic acid compound having a free ricinoleic acid carboxyl, is obtained in the manner previously described, or some obvious modification thereof. For instance, ricinoleic acid, diricinoleic acid, or triricinoleic acid, or a mixture thereof, is subjected to drastic oxidation and then to hydroxy-acetylation. The product is analyzed to determine its acid value. An alternate procedure is to employ a hydroxyacetylated, drastically-oxidized, dehydrated ricinoleic acid compound, and to subject it to acid saponification so as to yield the corresponding fatty acids. In any event, an oxyalkylated derivative, such as Example 1211) of Patent 2,541,991, is esterified with a hydroxyacetylated, drastically-oxidized dehydrated ricinoleic acid compound in acidic form, in an amount sufficient to convert approximately one-fourth of the polyglycol radicals into the fatty acid ester. The hydroxyl value of the oxyalkylated derivative can be calculated without determination, based on the hydroxyl value and weight of the phenol-aldehyde resin originally employed, plus the increase in weight after oxyalkylation. If glycide or methylglycide is employed, allowance must be made for the polyhydric character of the oxyalkylating reactant. In any event, if desired the hydroxyl value of the oxyalkylated product can be determined by the Verley-Bdlsing method, or any other acceptable procedure. The esterification recation is conducted in any conventional manner, such as that employed for the preparation of the higher fatty acid ester of phenoxyethanol.

Fatty acids of the kind described, i. e., hydroxylated, drastically-oxidized fatty acids show at least some solubility in the oxyalkylated derivatives of the kind shown in the previous examples,

65 temperature of 140 to 150 C. for approximately even though this is not necessarily true of the glycerides of the fatty acids. In this instance, reference is made to the oxyalkylated derivatives in absence of a solvent. Since esterification is best conducted in a system, it is our preference to add xylene or even a higher boiling solvent, such as mesitylene, cymene, tetralin or the like and conduct esterificationin such consolute mixture. It is not necessary to add all the fatty acid atone time. One may add aquarteror half the totalamount to be esterified, and after such por- 5 placed by an ester radical.

tial amount of xylene or higher boiling, waterinsoluble solvent, and to distill under a reflux condenser arrangement, so that water resulting from esterification is volatilized and condensed along with the xylene vapor in a suitably arranged trap. The amount of xylene employed is approximately equal to one-half the weight of the mixed reactants. The water should be removed from the trap, either manually or automatically, and the xylene returned continuously for further distillation. Such reaction is hastened if a small amount of dry hydrochloric acid gas is continuously injected into the esterification mixture. When the mixture is completed, the xylene is removed by distillation. Small amounts of unreacted specifically described fatty acid can be converted into the methyl or ethyl ester and removed by vacuum distillation, or permitted to remain. For example, an excess of anhydrous ethyl alchol may be added, and reacted so as to esterify any residual specifically described fatty acid, and then such excess of ethyl alcohol may be distilled off as a 95% alcohol-5% of water mixture, and thus the water resulting from esterification with the alchol can be removed.

However, even when the amount of specifically described fatty acid employed is stoichiometrically equal to the hydroxyl radicals presents, we have not found it desirable to take any undue 4o precautions to eliminate any residual specifically described fatty acid. As a matter of fact, numerous examples include the present one and those subsequently described which yield partial or fractional esters in which there are present residual hydroxyl radicals. Under such circumstances, there are substantially no free fatty acid radicals present, and the products obtained by partial esterification instead of complete esterification, represent the most valuable type. A

sulfonic acid, such as toluene sulfonic acid, may

be added in amounts of /2% to 1% to act as a catalyst.

The following ratios illustrate a specific example:

Grams Xylene-containing oxyalkylated resin 1211) of Patent 2,541,991 900 Product identified as Example 1 of Patent Xylene 150 Para-toluene sulfonic acid. 12

The above mixture was placed in a reflux vessel with appropriate condenser, and refluxed at a 4 to 6 hours, but in any event until the amount of water was at least equal to theoretical (4.5 cc.). Our experience has been, however, that due to moisture in the components or due to etherization, or for some other reason, the yield of water to thick, viscous liquids, and the color varies from a light amber-almost"water wliite toxa Theyare generally viscous liquidsrapt .toJaetacky anrlxsometimes show .a consistency just short :of

the sub-rubbery stage. The esters obtained :are,

apt to show physicaliproperties, as-fartas .viscosity andcolor go, somewhat intermediate betweenthe same properties .of the initial reactants. At times, they may be even more viscous :in :body and darker in appearance than either reactant. Part ofthis added darkening .is the result :of the sulfonic acid catalyst employed. .Inaigena eral wvay, :this characterizes all the :subsequent esters described, as far as .properties go, when the-z'solventis z-removed. Wegenera'lly remove a small amount of T the-sample, evaporate the solvent on a.stam bath overnight; and examine the residue. For most applications, zparticularly breaking of .oil fieldemulsions, the 'color immaterial 3 and there is no :real advantagein removingtm solvent. For Lthis reason no further comment will be :directed .to these particular properties. v

. 1:. .JEEmampZe Zd .The .same procedure was followed as in Example ld, preceding; except that the amount of described.hydroxyacetylated drastically-oxidized, dehydrated .ricinoleic acid compound fatty acid employed was sufficient to convertone-half of the polyglycolradicals into ester form.

.As aspeciflc example the following ratios were employed:

Grams Xylene-containing oxyal-k-ylated resin 123b of -Patent 2,541, 99-1 11329 Product identified as Example 2 of Patent Xylene 125 Para-toluene sulfonic acid 9 procedure followed Was that of Example 1d. The/reaction was stopped when 9 grams of water were eliminated. 7

Example 3d Xylene-containing oxyalkylated resin 11-71) "of-Patent 2.5413991 1075 Product identified as Example'3 of Patent 2',375',531 828 Xylene 200 Para-'toluene-sulfonic acid 12 Thel'samecproc'edure was followed as in'Examp'le .111 except that 14 grams of water were eliminated.

' Example 4d illhe same lprocedure was followed as in Example lcl, :preceding, except that the amount of described. hydroxyacetylated, drastically-oxidized. dehydrated ricinoleic-acid compound fatty acid employed was .sufiicicnt to convert substantially all of the .polyglycol radicals into ester form. a specific example the following ratios :were employed:

Grams Xylene-containing oxyalkylated resin 1'15b ofPatent'2,541;991 634 Product identified as Example 5 of Patent 2,375,531 1150 Xylene 200 Para-toluene sulfonic-acid, 20

The procedure followed was the 'sameas that in Example 1d, preceding, and the reaction was stopped when 20 gramsof water "had been eliminated.

' Example 5d The same procedure was followed asin Examples 1d to 4d, preceding, except that the oxyalkylated derivative, was exemplified by the example entitled 1051) of Patent 2,541,991. specific example the following ratios were used:

Grams Xylene-containing oxyalkylated resin 1051) .of'Patent 2,541;991 555 Product identified as Example 4 of Patent 2,375,531 5.50 Xylene 150 Para-toluene sulfonic acid 7.5

The procedure followed was the same as that described in Example 1d, and the'reaction continued until 9 cc. of water had been driven off.

Example 6d The same procedure was followed as in Examples 1d to 4d, preceding, except that 'the'oxyalkylated thermoplastic phenol-aldehyde resin is one of the type exemplified by Example 1 10b of Patent 2,541,991. In a specific example the following ratios were used:

Grams Xylene-containing oxyalkylated resin 1401) of Patent 2,541,991 "711 Product identified as Example 1 of Patent 2,375,531 975 Xylene 200 Para-toluene sulfonic acid 11 had been driven off.

Example 7d The same procedure was followed as in the preceding examples, except that the reactionwas conducted by means of the ethyl or methyl ester, instead of a corresponding acid. The ethyl or methyl ester can be obtained in any one of various ways. The previous description includes the hydroxyacetylation of the ethyl or methyl ester of dehydrated ricinoleic acid, dehydrated diricinoleic acid, or dehydrated triricinoleic acid, preceded by drastic oxidation. A procedure equally suitable was to obtain a similar derivative from the glyceride, to wit, a product of the kind described under the previous headings of Examples id to 5d, inclusive. Such product can be converted into the methyl or ethyl ester by the usual alcoholysis proceeding, employing anhydrous methyl alcohol, or anhydrous ethyl .alcohol, and a catalyst, such asan alkaline -mate-- rial. Such procedure was conventional, see for example, U. S. Patent Re. 22,751, reissued April 30, 1946, to Trent. I i-such procedure the liberated glycerol was discarded. We prefer to use the methyl or ethyl esterpbtained by the trans Ina position of a hydroxyacetylated, drastically oxidized, dehydrated tr'iricinolein. The reaction involving the second transposition with the .oxyalkylated thermoplastic resin, is preferably con ducted in the absence of any solvent, or if a solvent is employed, it should be fairly high boil ing, such as xylene. Instead of using an acid catalyst, an alkali such as caustic soda or sodium methylate is employed. The amount used varies from one-tenth of 1% to 1%. An average value may be in the neighborhood of one-half of 1%. The reaction was conducted preferably with the methyl ester which resulted in the eliminationof methanol. In the presence of a solvent, such as xylene, the methanol might distill over with the xylene and, if so, can be removed by washing with water, followed by removal of any moisture from the xylene with subsequent return of the xylene to the reaction vessel. However, any suitable procedure and any suitable catalyst may be employed so as to form the ester by elimination of low molal alcohol, particularly methanol. It is to be noted that by varying the amounts of the methyl ester added to the oxyalkylated resin one can introduce varying proportions of the acyl radical just as readily as if the acid itself were employed. It is intended, of course, to contemplate an entire range of such compounds comparable to those previously described. Obviously, completeness of reaction can be determined inany one of a number of ways, such as determination of the amount of low molal alcohol volatilized.

Example 811 The same procedure was followed as in the preceding examples, except that the esters produced by cross-esterification or trans-esterification, employing the glyceride so as to result in the formation of a non-volatile alcohol instead of a volatile alcohol as in the preceding examples. The catalyst employed was an alkaline catalyst, and the temperature employed was approximately 20-0 C. to 225 C. The time of reaction may vary somewhat, but generally requires 3 to 8 hours. The temperature should be high enough to insure trans-esterification in presence of the alkaline catalyst but, in any event, should be below the point of pyrolysis as far as the oxyalkylated derivative of fatty acid compound is concerned. As a rule, pyrolysis may take place at any temperature above 250 C. We prefer to conduct the reaction by simply employing derivatives of the kind described under the headings of Examples 1 to 5 of Patent 2,375,531, inclusive, and mix such reactants with the appropriate amount of oxyalkylated resins of the kind described, so that if reaction is coinplete and all the acyl groups originally attached to the glycerol radical become transposed to the polyglycerol radical, then by using variations of reactants, one will obtain the same range as described under the previous headings of Examples id to 6d. 7

In reactions of this kind with the liberation of a non-volatile alcohol, it is quite likely that the reaction does not go to completion. However, the equilibrium apparently permits a significant or substantial yield, due in part to the fact that the glycerol forms polyglycerols with comparative ease, whereas the hydroxyl radicals of the oxyalkylated derivatives may etherize to a lesser degree. There is also the possibility that in part the glycerol may etherize with the oxyalkylated derivative. This brings about the same where some of the oxyalkylated resins show moderate. or limited solubility in water prior to. es terification, particularly in the manner last indicated, they sometimes seem to show even greater solubility in water after such esterification process, notwithstanding the fact that apparently a large hydrophobe radical is introduced, and in essence, the repetitious alkylene linkage apparently must solubilize both hydrophobe radicals, i. e., the one derived from the resin and the one derived from the detergentforming monocarboxy acid. I

The solubility of the esters shows variation of substantially the same kind shown by the oxyethylated resins except, as a rule, any esterification tends to decrease solubility in water (subject to the exceptional instances noted in the preceding paragraph) and perhaps to a lesser extent in polar solvents tends to increase solubility in organic solvents, particularly in non-polar ,organic solvents. This is obvious insofar that the esters herein contemplated need not be total esters but may be fractional as well. Thus, the range of esters includes such wide variations in composition and solubilities.

As has been pointed out previously the esters as prepared in previous examples usually have a solvent, such as xylene or the like, present. Our preference is to leave such solvent present when the products are employed for demulsification or similar purposes. Needless to say, the solvent can be eliminated by evaporation or distillation, including vacuum distillation. If desired, the final product can be neutralized with ammonia or caustic potash or caustic soda to the methyl orange end point so as to eliminate the acidity clue to any sulfonic acid employed as a catalyst. If desired, any residual carboxyl acidity can be eliminated by further neutralization.

Attention is directed to the following fact. The oxyalkylated resins herein used as intermediate materials for further reaction to provide more complex derivatives are characterized by having certain minimum hydrophile properties as described, and it is particularly desirable that these hydrophile properties be sufiicient to produce an emulsion when mixed with xylene in the manner previously described.

Needless to say, when a derivative is formed, such derivative may have somewhat altered hydrophile character, or, stated another way, may have an altered hydrophobe-hydrophile balance. If an ester is prepared from a high molal acid, hydrophile character is increased. If such ester is prepared from sulio benzoic acid or the like, the hydrophile character may be enhanced. This is also true in even more complicated derivatives, such as the introduction of a quaternary nitrogen atom radical. In the formation of esters, the hydrophobe-hydrophile balance is aiiiected by the factor of whether one prepares a; complete or par-' tial ester. In a general way, although the herein described compounds are valuable for various purposes, particularly demulsification, even though the hydrophobe character may be increased somewhat and the hydrophile character decreased, yet when the same test is applied to the derivatives as is applied to the oxyalkylated resins and when such derivatives also show at least such minimum hydrophile character, they are unquestionably most advanta-= 9 geous, particularly for use as demulsifie'rs. Thus, in the hereto appended claims in pointing outthe invention in such specific character, at least part of the claims are directed to the derivatives in which the derivative meets the same final test in regard to the production of a xylene emulsion. Stated another way, the final derivative must be at least as hydrophile or more so than the minimum'- requirement for the oxyalkylated resin as defined.

We claim:

1. An ester in which the acyl radical is thatof the fatty acid of a hydroxyacetylated blown dehydrated ricinoleic acid compound selected from the class consisting of blown dehydrated castor oil, blown dehydrated triricinolein, blown dehydrated diricinolein, blown dehydrated monoricinolein, blown dehydrated ricinoleic acid, blown dehydrated polyricinoleic acid, and the estolides of blown dehydrated castor oil, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxya'lkylation products of (A) an alpha-beta alkylene oxide having: not more than 4. carbon atoms and selected from the class consisting" of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide, and (B) an oxyalkylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyalkylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (R) 71,, in which R1 is a member selected from the class consisting of ethylene 'radicals, propylene radicals, butylene radicals, hydroxypropylene radicals, and hydroxybutylene radicals, and n is a numeral varying from 1 to with the proviso that at least 2 moles of alkylene oxide be introduced for each phenolic nucleus.

2. An ester in which the acyl radical is that of the fatty acid of a hydroxyacetylated blown dehydrated ricinoleic acid compound selected from the class consisting of blown dehydrated castor oil, blown dehydrated triricinolein, blown dehydrated diricinolein, blown dehydrated monoricinolein, blown dehydrated ricinoleic acid, blown dehydrated polyricinoleic acid, and the estolides of blown dehydrated castor oil, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylation-susceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol. and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence-oi phenols of functionality greater than two; said phenol being of the formulain which R is a hydrocarbon radical having at least t and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule atthe phenolic hydroxyls of a plurality of divalent radicals having the formu a (CzHrOM; wherein n is a numeralvarying from I to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water. I

,3. An ester in. which the acyl radical" is that of the fatty acid of a hydroxyacetylated blown dehydrated ricinoleic acid compound selected from the class consisting of blown dehydrated castor oil, blown-deh drated triricinoleiii, blown dehydrated diriciriolein blown dehydrated monoricinolein, blown dehydrated ricinoleic acid, blown dehydrated polyricinoleic acid, and the estolides of blown dehydrated castor oil, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide, and (B) an oxyethylationsusceptible, fusible, organic solvent-soluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 7 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and having one functional group reactive toward said phenol; said resin being formed in the substantial absence of phenols of functionality greater than two said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality of divalent radicals having the formula (Cal-I40); wherein n is a numeral varying from 1 to 20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

4. An ester in which the acyl radical is that of the fatty acid of a hydroxyacetylated blown dehydrated ricinoleic acid compound selected from the class consisting of blown dehydrated susceptible, fusible, water-insoluble, low-stage phenol-formaldehyde resin having an average molecular weight cor- 'castor oil, blown dehydrated triricinolein, blown dehydrated diricinolein, blown dehydrated monoricinolein, blown dehydrated ricinoleic acid, blown dehydrated polyricinoleic acid, and the estolides of blown dehydrated castor oil, and the alcoholic radical is that of certain hydrophile polyhydric synthetic products; said hydrophile synthetic products being oxyethylation products of (A) ethylene oxide; and (B) an oxyethylationorganic solvent-soluble,

responding to atleast 3 and not over 7 phenolic nuclei per resin molecule; said resin being derived by reaction between a difunctional monohydric phenol and formaldehyde; said resin being formed in the substantial absence of phenols of functionality greater than two; said phenol being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 12 carbon atoms and substituted in one of the positions ortho and para; said oxyethylated resin being characterized by the introduction into the resin molecule at the phenolic hydroxyls of a plurality 1 to '20; with the proviso that at least 2 moles of ethylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyethylated resin, in an equal weight of xylene are sufficient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

5. The product of claim 3 wherein R is substituted in the para position.

6. The product of claim 3 wherein R is a butyl radical substituted in the para position.

'7. The product of claim 3 wherein R is an amyl radical substituted in the para position.

8. The product of claim 3 wherein R. is a nonyl radical substituted in the para position.

9. The product of claim 4 wherein R is substituted in the para position.

10. The product of claim 4 wherein Risa butyl radical substituted in the para position.

11. The product of claim 4 wherein R is an amyl radical substituted in the para position.

12. The product of claim 4 wherein R is a nonyl radical substituted in the para position.

. MELVIN DE GROOTE.

BERNHARD KEISER.

No references cited. 

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF A HYDROXYACETHYLATED BLOWN DEHYDRATED RICINOLEIC ACID COMPOUND SELECTED FROM THE CLASS CONSISTING OF BLOWN DEHYDRATES CASTOR OIL, BLOWN DEHYDRATED TRIRICINOLEIN, BLOWN DEHYDRATED DIRICINOLEIN, BLOWN DEHYDRATED MONORICINOLEIN, BLOWN DEHYDRATED RICINOLEIC ACID, BLOWN DEHYDRATED POLYRICINOLEIC ACID, AND THE ESTOLIDES OF BLOWN DEHYDRATED CASTOR OIL, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFINCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUP REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEING OF THE FORMULA 